Triethylamine → HCID 59385241, compound

HRID 2356820Notes

Reaction equation

HRID 2356820 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][C:7]([C:10]2[CH:15]=[CH:14][C:13]([C:16]([OH:18])=O)=[CH:12][CH:11]=2)=[CH:6][CH:5]=1)([O-:3])=[O:2].C(Cl)(=O)C(Cl)=O.Cl.[CH3:26][NH:27][C@H:28]([C:32]([O:34][CH3:35])=[O:33])[CH:29]([CH3:31])[CH3:30].C(N(CC)CC)C>C(Cl)Cl.CN(C)C=O>[CH3:26][N:27]([C:16]([C:13]1[CH:12]=[CH:11][C:10]([C:7]2[CH:6]=[CH:5][C:4]([N+:1]([O-:3])=[O:2])=[CH:9][CH:8]=2)=[CH:15][CH:14]=1)=[O:18])[C@H:28]([C:32]([O:34][CH3:35])=[O:33])[CH:29]([CH3:31])[CH3:30]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 66723[1,1'-Biphenyl]-4-carboxylic acid, 4'-nitro-HCID 13819431HCID 13819431, compound

Product 1

HCID 59385241HCID 59385241, compoundYield 94.5%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideCatalystHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
50 °C

Procedure

4′-Nitro-1,1′-biphenyl-4-carboxylic acid (0.50 g, 2.0 mmol) was dissolved in methylene chloride (25 mL), and then oxalyl chloride (0.27 mL, 3.1 mmol) was added, followed by one drop of N,N-dimethylformamide. The resulting mixture was heated at 50° C. for 1 h, concentrated under reduced pressure, and further dried under vacuum for 30 min. The residue was dissolved in methylene chloride (20 mL) and added dropwise to an ice-cold mixture of methyl N-methyl-L-valinate hydrochloride (0.48 g, 2.6 mmol), methylene chloride (50 mL), and triethylamine (1.44 mL, 10.2 mmol). The resulting solution was stirred on ice for 1 h and then at rt overnight. The mixture was diluted with methylene chloride and washed with 1N aqueous HCl solution and brine. The organic layer was separated and concentrated under reduced pressure. The residue was purified by flash chromatography (Biotage® system, 3:1 hexanes/EtOAc) to afford methyl N-methyl-N-[(4′-nitro-1,1′-biphenyl-4-yl)carbonyl]-L-valinate (0.70 g, 92%). 1H NMR (400 MHz, CDCl3) δ 0.85 (dd, 3H), 1.06 (dd, 3H), 2.31 (m, 1H), 3.02 (d, 3H), 3.77 (d, 3H), 3.94 (d, 0.5H), 4.98 (d, 0.5H), 7.52 (m, 2H), 7.64 (m, 2H), 7.72 (t, 2H), 8.27 (d, 2H); LC-MS m/z 371.2 (MH+), retention time 3.27 minutes.

Workup

  1. concentrationconcentrated under reduced pressure
  2. customfurther dried under vacuum for 30 min
  3. dissolutionThe residue was dissolved in methylene chloride (20 mL)
  4. customat rt
  5. customovernight
  6. washwashed with 1N aqueous HCl solution and brine
  7. customThe organic layer was separated
  8. concentrationconcentrated under reduced pressure
  9. customThe residue was purified by flash chromatography (Biotage® system, 3:1 hexanes/EtOAc)

Sources & evidence

ORD record
ord-ff6ec0d40b9e4c66805a842fd38bad78
Source dataset
uspto-grants-2010_07
Patent number
US07759376B2

Reaction notes

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